Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
  • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

• the present invention relates generally to polymerizable monomers which comprise at least one 1- or 2-propylene moiety and further comprise both aromatic moieties and additional aliphatic moieties and to resins and thermoset products based on these monomers.
• thermosetting resins used in electrical applications continue to escalate.
• high frequency electronics have become more commonplace with advances in computer, communications, and wireless technologies.
• resins which show reduced dielectric constants and dissipation factors as well as enhanced thermal resistance.
• Aromatic cyanate esters have been used in electronics applications for many years.
• the most common cyanate ester, bisphenol A dicyanate is prepared by reaction of bisphenol A (isopropylidene diphenol) with a cyanogen halide, for example, cyanogen bromide, in the presence of an acid acceptor, for example, triethylamine.
• thermoset resins with desired property improvements has involved development of copolymerizable mixtures of aromatic cyanate esters and one or more other monomers. Most commonly encountered are the copolymers of aromatic cyanate esters and bis(maleimides). Also known are copolymers of aromatic cyanate esters (or aromatic cyanamides) with ethylenically unsaturated polymerizable monomers including allyl monomers, with diallyl bisphenol A being most notable.
• thermosets produced from di- and polycyanates can be improved by increasing the hydrocarbon content of the thermoset matrix.
• One such method is to increase the hydrocarbon content of the di- or polycyanate monomer used.
• the present inventors have now found another method for increasing the hydrocarbon content of the thermoset matrix, i.e., through the use of hydrocarbon-rich polymerizable ethylenically unsaturated monomers which can be copolymerized with, e.g., cyanate monomers.
• the present inventors have found, inter alia, a class of monomers which contain a high percentage of non-polar hydrocarbon groups. While the art might have predicted that the incorporation of a hydrocarbon structure would be deleterious to the thermal properties and the cure profile of a thermosettable mixture incorporating these monomers, the exact opposite was observed (see Examples and Comparative Experiments below). Thus, the hydrocarbon portion of the monomers was found to be desirable because it affords enhanced thermal resistance, low moisture absorption, and excellent dielectric properties, without a deleterious effect on the cure behavior of a thermosettable mixture prepared therefrom. It was unexpectedly found that the increased hydrocarbon content of the monomers of the present invention can moderate the enthalpic cure energy without increasing the cure onset and end temperatures. This reduction in exothermicity on cure can help to prevent damage such as cracking or delamination which may result from the cure of monomers which comprise a smaller proportion of non-polar hydrocarbon groups than the monomers of the present invention.
• the present invention provides ethylenically unsaturated monomers of formula (I):
• the monomers of formula (I) may be ethylenically unsaturated monomers of formula (Ia):
• n has a value of from about 5 to about 24; each m independently is 0, 1, or 2; the moieties R independently represent halogen, cyano (-CN), nitro, hydroxy, amino optionally carrying one or two alkyl groups preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkyl preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted cycloalkyl preferably having from about 5 to about 8 carbon atoms, unsubstituted or substituted alkoxy preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkenyl preferably having from
• any non-aromatic cyclic moieties comprised in the above formula (Ia) may optionally carry one or more substituents and/or may optionally comprise one or more double bonds and/or may optionally be polycyclic.
• n may have a value of from about 9 to about 16; for example, n may have a value of 9, 10, or 11 and may in particular equal 11.
• each m may independently be 0 or 1.
• the moieties R 1 may independently represent hydrogen or methyl.
• Non-limiting examples of the monomers of formula (I) include l,l-bis(4- hydroxyphenyl)cyclododecane bis(allyl ether), l,l-bis(4-hydroxyphenyl)- cyclododecane bis(methallyl ether), l,l-bis(4-hydroxyphenyl)cyclodecane bis(allyl ether), l,l-bis(4-hydroxyphenyl)cyclodecane bis(methallyl ether), 2,2-bis(4- hydroxyphenyl)adamantane bis(allyl ether), 2,2-bis(4-hydroxyphenyl)adamantane bis(methallyl ether), 4,4'-bis(4-hydroxyphenyl)octahydro-l,4:5,8-
• the present invention also provides ethylenically unsaturated monomers of formula (II):
• any non-aromatic cyclic moieties comprised in the above formula (II) may optionally carry one or more substituents and/or may optionally comprise one or more double bonds.
• p may have a value of from 1 to about 14.
• p may have a value of 1, 2, or 3 and may in particular equal 1.
• each m may independently be 0 or 1.
• the moieties Q may independently represent
• HR 1 C CR ⁇ CH 2 - or HaR ⁇ -CR ⁇ HC-.
• the moieties R 1 may independently represent hydrogen or methyl.
• the moieties Q may be identical and represent allyl
• Non-limiting examples of the monomers of the above formula (II) include dimethylcyclohexane tetraphenol tetra(allyl ether), dimethylcyclohexane tetraphenol tetra(methallyl ether), dimethylcyclohexane tetraphenol tetra( 1-propenyl ether), dimethylcyclooctane tetraphenol tetra(allyl ether), dimethylcyclooctane tetraphenol tetra(methallyl ether), dimethylcyclooctane tetraphenol tetra( 1-propenyl ether), partial or complete Claisen rearrangement products of dimethylcyclohexane tetraphenol tetra(allyl ether), and monomers which carry at least one substituent on at least one aromatic ring to block a Claisen rearrangement.
• a preferred example of the monomers of formula (II) is dimethylcyclohexan
• the present invention also provides polymers (i.e., homo- and copolymers) and prepolymers of the ethylenically unsaturated monomers of formulae (I)/(Ia) and (II) set forth above (including the various aspects thereof).
• the present invention also provides a first polymerizable mixture which comprises at least two of (i) at least one monomer of the above formula (I)/(Ia) and/or a prepolymer thereof, (ii) at least one monomer of the above formula (II) and/or a prepolymer thereof, and
• the at least one monomer (iii) may be selected from monomers which comprise one or more polymerizable ethylenically unsaturated moieties, aromatic di- and polycyanates, aromatic di- and polycyanamides, di- and polymaleimides, and di- and polyglycidyl ethers.
• the first mixture may comprise at least components (i) and (iii), or it may comprise at least components (ii) and (iii).
• component (iii) of the first mixture may comprise a dicyanate compound of the following formula (III) and/or a prepolymer thereof:
• n has a value of from about 5 to about 24; each m independently is 0, 1, or 2; the moieties R independently represent halogen, cyano, nitro, unsubstituted or substituted alkyl preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted cycloalkyl preferably having from about 5 to about 8 carbon atoms, unsubstituted or substituted alkoxy preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkenyl preferably having from 3 to about 6 carbon atoms, unsubstituted or substituted alkenyloxy preferably having from 3 to about 6 carbon atoms, unsubstituted or substituted aryl preferably having from 6 to about 10 carbon atoms, unsubstituted or substituted aralkyl preferably having from 7 to about
• any non-aromatic cyclic moieties comprised in the above formula (III) may optionally carry one or more substituents and/or may optionally comprise one or more double bonds and/or may optionally be polycyclic.
• n may have a value of from about 9 to about 16.
• n may have a value of 9, 10, or 11 and may in particular equal 11.
• each m may independently be 0 or 1.
• dicyanate compound of formula (III) is l,l-bis(4- cyanatophenyl)cyclododecane.
• component (iii) thereof may comprise a polycyanate compound of formula (IV) and/or a prepolymer thereof:
• all four moieties Q may represent -CN.
• each m may independently be 0 or 1 and/or p may have a value of from 1 to about 14.
• p may have a value of 1, 2, or 3 and may in particular equal 1.
• a specific example of a polycyanate compound of formula (IV) is dimethylcyclohexane tetraphenol tetracyanate.
• the mixture may further comprise one or more substances which are selected from polymerization catalysts, co-curing agents, flame retardants, synergists for flame retardants, solvents, fillers, adhesion promoters, wetting aids, dispersing aids, surface modifiers, thermoplastic polymers, and mold release agents.
• the present invention also provides a second mixture which comprises at least one ethylenically unsaturated monomer of the above formula (I)/(Ia) and/or a prepolymer thereof and one or more substances which are selected from polymerization catalysts, co- curing agents, flame retardants, synergists for flame retardants, solvents, fillers, adhesion promoters, wetting aids, dispersing aids, surface modifiers, thermoplastic polymers, and mold release agents.
• the second mixture may be substantially free of polymerizable monomers and/or monomers which are copolymerizable with the at least one ethylenically unsaturated monomer of the above formula (I)/(Ia).
• the present invention also provides a third mixture which comprises at least one ethylenically unsaturated monomer of the above formula (II) and/or a prepolymer thereof and one or more substances which are selected from polymerization catalysts, co-curing agents, flame retardants, synergists for flame retardants, solvents, fillers, glass fibers, adhesion promoters, wetting aids, dispersing aids, surface modifiers, thermoplastic polymers, and mold release agents.
• substances which are selected from polymerization catalysts, co-curing agents, flame retardants, synergists for flame retardants, solvents, fillers, glass fibers, adhesion promoters, wetting aids, dispersing aids, surface modifiers, thermoplastic polymers, and mold release agents.
• each of the first, second and third mixtures set forth above may be partially polymerized (e.g., prepolymerized or B-staged) or completely polymerized and the present invention also provides a product which comprises such a partially or completely polymerized (preferably substantially completely polymerized) mixture.
• the product or part thereof may be an electrical laminate, an IC (integrated circuit) substrate, a casting, a coating, a die attach and mold compound formulation, a composite, and an adhesive.
• the present invention also provides a process for preparing a mixture of ethylenically unsaturated monomers, which mixture may, for example, comprise one or more of the ethylenically unsaturated monomers of the above formula (II).
• the process comprises the condensation of a dialdehyde of a cycloalkane having from about 5 to about 24 ring carbon atoms with a hydroxyaromatic (e.g., phenolic) compound at a ratio of aromatic hydroxy groups to aldehyde groups which affords a mixture of polyphenolic compounds with a polydispersity of not higher than about 2, e.g., not higher than about 1.8, not higher than about 1.5, or not higher than about 1.3.
• a hydroxyaromatic e.g., phenolic
• the ratio of the number of aromatic hydroxy groups to the number of aldehyde groups may be at least about 4, e.g., at least about 5, at least about 5.5, or at least about 6.
• the cycloalkane may have from about 6 to about
• 19 ring carbon atoms for example, 6, 7, or 8 ring carbon atoms and in particular 6 ring carbon atoms.
• the dialdehyde may comprise a cyclohexane dicarboxaldehyde
• 1,3-cyclohexane dicarboxaldehyde and/or 1,4-cyclohexane dicarboxaldehyde and/or the hydroxyaromatic compound may comprise phenol.
• the moieties R 1 may independently represent hydrogen or methyl.
• the groups of formula HR 1 C CR 1 -
• CH 2 -O- and/or may represent allyl, methallyl, or 1-propenyl.
• the present invention also provides a mixture of ethylenically unsaturated monomers which are obtainable by the process set forth above (including the various aspects thereof), either as such, or in partially polymerized (e.g., prepolymerized or B- staged) or completely polymerized and/or partially or completely copolymerized form.
• the polydispersity of the mixture may be not higher than about 1.8, e.g., not higher than about 1.5, or not higher than about 1.3, and/or the average number of hydroxy groups per molecule may be at least about 4, e.g., at least about
• a reference to a compound or component includes the compound or component by itself, as well as in combination with other compounds or components, such as mixtures of compounds.
• the present invention provides, inter alia, ethylenically unsaturated monomers of formula (I):
• the moieties R a and R b in the above formula (I) may independently represent optionally substituted aliphatic groups comprising a total of from about 5 to about 24 carbon atoms. Usually, the total number of carbon atoms in the aliphatic moieties R a and R b will be at least about 6, e.g., at least about 7, at least about 8, at least about 9, or at least about 10, but will usually be not higher than about 18, e.g., not higher than about 16, or not higher than about 12.
• the aliphatic moieties may be linear, branched or cyclic and saturated or unsaturated.
• Non-limiting examples thereof are linear or branched alkyl groups and alkenyl groups, cycloalkyl and cycloalkenyl groups as well as alkylcycloalkyl and cycloalkylalkyl groups such as, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n- decyl, n-undecyl, n-dodecyl, cyclohexyl, methylcyclohexyl, and cyclohexylmethyl, and the corresponding mono- and diunsaturated groups.
• these groups may be substituted by one or more (e.g., 1, 2, 3, or 4) substituents.
• substituents are F, Cl and Br, as well as aromatic groups (such as, e.g., phenyl).
• aromatic groups such as, e.g., phenyl.
• R a and R b will represent methyl or ethyl, in particular, methyl.
• the moieties R a and R b in the above formula (I) may also form, together with the carbon atom to which they are bonded, an optionally unsaturated and/or optionally substituted and/or optionally polycyclic aliphatic ring structure which has at least about 6 ring carbon atoms.
• Examples of corresponding compounds are those of formula (Ia):
• n in the above formula (Ia) is not lower than about 5, e.g., not lower than about 6, not lower than about 7, not lower than about 8, not lower than about 9, or not lower than about 10, and not higher than about 24, e.g., not higher than about 16, not higher than about 14, or not higher than about 12, and preferably equals 8, 9, 10, 11, or 12, in particular 11 (i.e., giving rise to a cyclododecylidene structure).
• the cycloaliphatic moiety shown in the above formula (Ia) may optionally comprise one or more (e.g., 1, 2, 3, or 4) double bonds and/or may carry one or more (e.g., 1, 2, or 3) substituents and/or may optionally be polycyclic (e.g., bicyclic or tricyclic). If more than one substituent is present, the substituents may be the same or different.
• Non-limiting examples of substituents which may be present on the cycloaliphatic moiety are alkyl groups, e.g., optionally substituted alkyl groups having from 1 to about 6 carbon atoms (e.g., methyl or ethyl), hydroxy, amino which optionally carries one or two alkyl groups preferably having from 1 to about 6 carbon atoms and halogen atoms such as, e.g., F, Cl, and Br.
• the alkyl groups may be substituted with, for example, one or more halogen atoms such as, e.g., F, Cl, and Br.
• the value of each m in the above formula (I)/(Ia) independently is 0, 1, or 2.
• the values of m are identical and/or are 0 or 1.
• the moieties R in the above formula (I)/(Ia) independently represent halogen (e.g., F, Cl, and Br, preferably Cl or Br), cyano, nitro, hydroxy, amino optionally carrying one or two alkyl groups preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkyl preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted cycloalkyl preferably having from about 5 to about 8 carbon atoms, unsubstituted or substituted alkoxy preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkenyl preferably having from 3 to about 6 carbon atoms, unsubstituted or substituted alkenyloxy preferably having from 3 to about 6 carbon atoms, unsubstituted or substituted aryl preferably having from 6 to about 10 carbon atoms, unsubstituted or substituted aralkyl preferably having from 7
• alkyl and alkenyl are used in the present specification and the appended claims, these terms also include the corresponding cycloaliphatic groups such as, e.g., cyclopentyl, cyclohexyl, cyclopentenyl, and cyclohexenyl.
• cycloaliphatic groups such as, e.g., cyclopentyl, cyclohexyl, cyclopentenyl, and cyclohexenyl.
• two alkyl and/or alkenyl groups are attached to two (preferably adjacent) carbon atoms of an aliphatic or aromatic ring, they may be combined to form an alkylene or alkenylene group which together with the carbon atoms to which this group is attached results in a preferably 5- or 6- membered ring structure. In the case of non-adjacent carbon atoms, this ring structure may give rise to a bicyclic compound.
• the above alkyl groups R (including the alkyl groups which may be present in the above amino group which may carry one or two alkyl groups) and alkoxy groups will often comprise from 1 to about 4 carbon atoms and in particular, 1 or 2 carbon atoms.
• Non-limiting specific examples of these groups include, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy.
• the alkyl and alkoxy groups may be substituted with one or more (e.g., 1, 2, or 3) substituents. If more than one substituent is present, the substituents may be the same or different and are preferably identical. Non-limiting examples of these substituents include halogen atoms such as, e.g., F, Cl, and Br. Non-limiting specific examples of substituted alkyl and alkoxy groups include CF 3 , CF 3 CH 2 , CCl 3 , CCl 3 CH 2 , CHCl 2 , CH 2 Cl, CH 2 Br, CCl 3 O, CHCl 2 O, CH 2 ClO, and CH 2 BrO.
• substituents include halogen atoms such as, e.g., F, Cl, and Br.
• substituted alkyl and alkoxy groups include CF 3 , CF 3 CH 2 , CCl 3 , CCl 3 CH 2 , CHCl 2 , CH 2 Cl, CH 2 Br, CCl 3
• the above alkenyl and alkenyloxy groups will often comprise 3 or 4 carbon atoms and in particular, 3 carbon atoms. Non-limiting specific examples of these groups are allyl, methallyl, and 1-propenyl.
• the alkenyl and alkenyloxy groups may be substituted with one or more (e.g., 1, 2, or 3) substituents. If more than one substituent is present, the substituents may be the same or different and are preferably identical. Non-limiting examples of these substituents include halogen atoms such as, e.g., F, Cl, and Br.
• the above aryl and aryloxy groups will often be phenyl and phenoxy groups.
• the aryl and aryloxy groups may be substituted with one or more (e.g., 1, 2, 3, 4, or 5) substituents. If more than one substituent is present, the substituents may be the same or different.
• Non-limiting examples of these substituents include hydroxy, nitro, cyano, halogen such as, e.g., F, Cl, and Br, optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl), optionally halogen- substituted alkoxy having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methoxy or ethoxy), and amino which may optionally carry one or more alkyl groups having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl).
• halogen such as, e.g., F, Cl, and Br
• optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms e.g., from 1 to about 4 carbon
• Non-limiting specific examples of substituted aryl and aryloxy groups include, tolyl, xylyl, ethylphenyl, chlorophenyl, bromophenyl, tolyloxy, xylyloxy, ethylphenoxy, chlorophenoxy, and bromophenoxy.
• aralkyl and aralkoxy groups will often be benzyl, phenethyl, benzyloxy, or phenethoxy groups. These groups may be substituted (preferably on the aryl ring, if at all) with one or more (e.g., 1, 2, 3, 4, or 5) substituents. If more than one substituent is present, the substituents may be the same or different.
• Non-limiting examples of these substituents include hydroxy, nitro, cyano, halogen such as, e.g., F, Cl, and Br, optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl), optionally halogen-substituted alkoxy having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methoxy or ethoxy), and amino which may optionally carry one or more alkyl groups having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl).
• halogen such as, e.g., F, Cl, and Br
• optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms e.g., from 1 to about
• a preferred moiety Q is allyl.
• Non-limiting specific examples of the above alkyl moieties R 1 include methyl, ethyl, propyl, and isopropyl. Methyl is preferred. If one or more substituents are present on these alkyl groups they may, for example, be halogen such as, e.g., F, Cl, and Br.
• Non-limiting examples of the above monomers of formula (I)/(Ia) include l,l-bis(4-hydroxyphenyl)cyclododecane bis(allyl ether), l,l-bis(4-hydroxyphenyl)- cyclododecane bis(methallyl ether), l,l-bis(4-hydroxyphenyl)-cyclododecane bis(l- propenyl ether), l,l-bis(4-hydroxyphenyl)cyclodecane bis(allyl ether), l,l-bis(4- hydroxyphenyl)cyclodecane bis(methallyl ether), l,l-bis(4-hydroxyphenyl)- cyclodecane bis(l -propenyl ether), 2,2-bis(4-hydroxyphenyl)adamantane bis(allyl ether), 2,2-bis(4-hydroxyphenyl)adamantane bis(methallyl ether), 4,4
• Claisen rearrangement products include compounds of formulae (A) and (B):
• the monomers of formula (I)/(Ia) may prepared by methods which are well known to those of skill in the art. For example, these monomers may be prepared by etherification of a bisphenol of formula (V):
• the bisphenol of formula (V) can be prepared, for example, by condensation of phenols with ketones using methods well known in the art. Examples of these methods are described in, e.g., U.S. Patent No. 4,438,241 and DE 3345945, the entire disclosures whereof are incorporated by reference herein.
• the ketone is usually treated with a large excess of a phenol in the presence of an acid catalyst, non-limiting examples of which include mineral acids such as HCl or H 2 SO 4 , arylsulfonates, oxalic acid, formic acid, or acetic acid.
• an acid catalyst non-limiting examples of which include mineral acids such as HCl or H 2 SO 4 , arylsulfonates, oxalic acid, formic acid, or acetic acid.
• a cocatalyst such as, e.g., a mercaptan may be added.
• a bed of sulfonated crosslinked polystyrene beads it is also common to use a bed of sulfonated crosslinked polystyrene beads.
• Non-limiting examples of suitable ketone starting materials include cycloaliphatic ketones such as, e.g., cyclohexanone, 2-bromocyclohexanone, 2- chlorocyclohexanone, 2-methyl-cyclohexanone, 3-methylcyclohexanone, A- methylcyclohexanone, 2-isopropylcyclohexanone, 3-isopropylcyclohexanone, A- isopropylcyclohexanone, 2-n-butylcyclohexanone, 3-n-butylcyclohexanone, 4-n- butylcyclohexanone, 2-sec-butylcyclohexanone, 3-sec-butylcyclohexanone, 4-sec- butylcyclohexanone, 2-isobutylcyclohexanone, 3-isobutylcyclohexanone, A- isobutylcyclohexanone, 2-t-butylcyclo
• Non-limiting examples of suitable phenol starting materials include phenol, ⁇ -cresol, m-cresol, p-cresol, o-chlorophenol, o- bromophenol, 2-ethylphenol, 2-octylphenol, 2-nonylphenol, 2,6-xylenol, 2-t-butyl-5- methylphenol, 2-t-butyl-4-methylphenol, 2,4-di(t-butyl)phenol, 2-t-butylphenol, 2-sec- butylphenol, 2-n-butylphenol, 2-cyclohexylphenol, 4-cyclohexylphenol, 2-cyclohexyl-5- methylphenol, ⁇ -decalone, and ⁇ -decalone.
• this condensation chemistry can give a mixture of products such as o-alkylation of the phenol, oligomers derived from multiple alkylation of the phenol by the ketone, and acid-catalyzed rearrangement products.
• These impurities can either be removed or left in the material used as starting material for the cyanation reaction.
• these impurities can be beneficial, in that they lower the melting point of the final cyanated product. This can make it easier to prepare to formulate the cyanate by making it more soluble and reducing the tendency to crystallize.
• the presence of the oligomers tends to increase the viscosity of the cyanate and therefore its formulated products. This can be a beneficial or harmful property depending on the application.
• the allylation of a bisphenol of formula (V) may be accomplished via a transcarbonation reaction using, for example, allyl methyl carbonate or a direct allylation reaction using, for example, an allyl halide, a methallyl halide and the like plus an alkaline agent and optional catalyst such as a phase transfer catalyst.
• Allyl methyl carbonate is usually prepared from the reaction of allyl alcohol and dimethyl carbonate to give a mixture of allyl methyl carbonate and diallyl carbonate.
• Both the crude mixture and the pure allyl methyl carbonate can be used as the allylating agent as well as allyl halides such as allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, and the like.
• a preferred process uses a transcarbonation reaction wherein allyl methyl carbonate is stoichiometrically reacted with a bisphenol of formula (V) and provides essentially total allylation of the hydroxy groups of the bisphenol to provide the corresponding allylether (allyloxy) groups.
• a bisphenol of formula (V) provides essentially total allylation of the hydroxy groups of the bisphenol to provide the corresponding allylether (allyloxy) groups.
• an allyl halide may be stoichiometrically reacted with the hydroxy groups of the bisphenol.
• variable amounts of Claisen rearrangement product may be observed in this reaction, resulting in mixtures of O- and C-allylated products.
• a direct allylation reaction of the bisphenol of formula (V) with an allyl halide such as allyl chloride may, for example, be conducted in the presence of an alkaline agent such as an aqueous solution of an alkali metal hydroxide (e.g., NaOH).
• an alkaline agent such as an aqueous solution of an alkali metal hydroxide (e.g., NaOH).
• inert solvents such as, e.g., 1,4-dioxane
• phase transfer catalysts such as, e.g., benzyltrialkylammonium halides or tetraalkylammonium halides can be employed.
• Reaction temperatures of from about 25° to about 15O 0 C are operable with temperatures of from about 50° to about 100 0 C being preferred.
• Reaction times of from about 15 minutes to about 8 hours are operable with reaction times of from about 2 hours to about 6 hours being preferred.
• the reaction of less than a 1 to 1 mole ratio of allyl methyl carbonate in the transcarbonation reaction or of allyl halide in the direct allylation reaction with the hydroxy groups of the bisphenol will provide partial allylation of the bisphenol with some free hydroxy groups remaining. Although these partially allylated bisphenol compositions are less preferred, they are still useful as compositions of the present invention.
• the present invention also provides ethylenically unsaturated monomers of formula (II):
• p is 0 or an integer of from 1 to about 19, e.g., up to about 14, up to about 12, or up to about 8 such as, e.g., 1, 2, 3, 4, 5, 6, and 7, with 1, 2, or 3 being preferred and 1 being particularly preferred.
• the cycloaliphatic moiety shown in the above formula (II) may comprise one or more (e.g., 1, 2, 3, or 4) double bonds and/or may carry one or more (e.g., 1, 2, or 3) substituents (although the cycloaliphatic moiety will usually not comprise any double bonds and/or substituents). If more than one substituent is present, the substituents may be the same or different.
• Non-limiting examples of substituents which may be present on the cycloaliphatic moiety are alkyl groups, e.g., optionally substituted alkyl groups having from 1 to about 6 carbon atoms (e.g., methyl or ethyl), hydroxy, amino optionally carrying one or two alkyl groups having from 1 to about 6 carbon atoms, and halogen atoms such as, e.g., F, Cl, and Br.
• the alkyl groups may be substituted with, e.g., one or more halogen atoms such as, e.g., F, Cl, and Br.
• each m in the above formula (II) independently is 0, 1, or 2.
• the values of m are identical and/or are 0 or 1.
• the moieties R in the above formula (II) independently represent halogen (e.g., F, Cl, and Br, preferably Cl or Br), cyano, nitro, hydroxy, amino optionally carrying one or two alkyl groups preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkyl preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted cycloalkyl preferably having from about 5 to about 8 carbon atoms, unsubstituted or substituted alkoxy preferably having from 1 to about 6 carbon atoms, unsubstituted or substituted alkenyl preferably having from 3 to about 6 carbon atoms, unsubstituted or substituted alkenyloxy preferably having from 3 to about 6 carbon atoms, unsubstituted or substituted aryl preferably having from 6 to about 10 carbon atoms, unsubstituted or substituted aralkyl preferably having from 7 to about 12 carbon
• the above alkyl groups (including the alkyl groups which may be present in the above amino group which may carry one or two alkyl groups) and alkoxy groups will often comprise from 1 to about 4 carbon atoms and in particular, 1 or 2 carbon atoms.
• Non-limiting specific examples of these groups include, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy.
• the alkyl and alkoxy groups may be substituted with one or more (e.g., 1, 2, or 3) substituents. If more than one substituent is present, the substituents may be the same or different and are preferably identical. Non-limiting examples of these substituents include halogen atoms such as, e.g., F, Cl, and Br. Non-limiting examples of substituted alkyl and alkoxy groups include CF 3 , CF 3 CH 2 , CCl 3 , CCl 3 CH 2 , CHCl 2 , CH 2 Cl, CH 2 Br, CCl 3 O, CHCl 2 O, CH 2 ClO, and CH 2 BrO.
• substituents include halogen atoms such as, e.g., F, Cl, and Br.
• substituted alkyl and alkoxy groups include CF 3 , CF 3 CH 2 , CCl 3 , CCl 3 CH 2 , CHCl 2 , CH 2 Cl, CH 2 Br, CCl 3 O
• the above alkenyl and alkenyloxy groups will often comprise 3 or 4 carbon atoms and in particular, 3 carbon atoms. Non-limiting specific examples of these groups are allyl, methallyl, and 1-propenyl.
• the alkenyl and alkenyloxy groups may be substituted with one or more (e.g., 1, 2, or 3) substituents. If more than one substituent is present, the substituents may be the same or different and are preferably identical. Non-limiting examples of these substituents include halogen atoms such as, e.g., F, Cl, and Br.
• the above aryl and aryloxy groups will often be phenyl and phenoxy groups.
• the aryl and aryloxy groups may be substituted with one or more (e.g., 1, 2, 3, 4, or 5) substituents. If more than one substituent is present, the substituents may be the same or different.
• Non-limiting examples of these substituents include hydroxy, nitro, cyano, halogen such as, e.g., F, Cl, and Br, optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl), optionally halogen- substituted alkoxy having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methoxy or ethoxy), and amino which may optionally carry one or more alkyl groups having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl).
• halogen such as, e.g., F, Cl, and Br
• optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms e.g., from 1 to about 4 carbon
• Non-limiting specific examples of substituted aryl and aryloxy groups include, tolyl, xylyl, ethylphenyl, chlorophenyl, bromophenyl, tolyloxy, xylyloxy, ethylphenoxy, chlorophenoxy, and bromophenoxy.
• aralkyl and aralkoxy groups will often be benzyl, phenethyl, benzyloxy, or phenethoxy groups. These groups may be substituted (preferably on the aryl ring, if at all) with one or more (e.g., 1, 2, 3, 4, or 5) substituents. If more than one substituent is present, the substituents may be the same or different.
• Non-limiting examples of these substituents include hydroxy, nitro, cyano, halogen such as, e.g., F, Cl, and Br, optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl), optionally halogen-substituted alkoxy having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methoxy or ethoxy), and amino which may optionally carry one or more alkyl groups having from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl or ethyl).
• halogen such as, e.g., F, Cl, and Br
• optionally halogen-substituted alkyl having from 1 to about 6 carbon atoms e.g., from 1 to about
• the moieties R 1 independently represent hydrogen or unsubstituted or substituted (preferably unsubstituted) alkyl having from 1 to about 3 carbon atoms.
• a preferred moiety Q is allyl.
• the moieties Q it is preferred for the moieties Q to be identical and/or to be different from hydrogen.
• Preferably at least one of the moieties Q is different from hydrogen. Even more preferred, at least two or at least three moieties Q are different from hydrogen.
• Non-limiting specific examples of the above alkyl moieties R 1 include methyl, ethyl, propyl and isopropyl. Methyl is preferred. If one or more substituents are present in these alkyl groups they may, for example, be halogen such as, e.g., F, Cl, and Br.
• Non-limiting examples of the above monomers of formula (II) include dimethylcyclohexane tetraphenol tetra(allyl ether), dimethylcyclohexane tetraphenol tetra(methallyl ether), dimethylcyclohexane tetraphenol tetra(l-propenyl ether), dimethylcyclooctane tetraphenol tetra(allyl ether), dimethylcyclooctane tetraphenol tetra(methallyl ether), dimethylcyclooctane tetraphenol tetra(l-propenyl ether), partial or complete Claisen rearrangement products of dimethylcyclohexane tetraphenol tetra(allyl ether), and monomers which carry at least one substituent on at least one aromatic ring to block a Claisen rearrangement.
• cyclohexane (1,3 and/or l,4)-dicarboxaldehyde can be produced, e.g., by hydroformylation of a cyclohexene carboxaldehyde, which in turn can be prepared by a Diels-Alder reaction of a conjugated diene such as, e.g., butadiene, piperylene, isoprene and chloroprene with an optionally substituted alpha,beta-unsaturated aldehyde such as, e.g., acrolein, methacrolein, crotonaldehyde or cinnamaldehyde as the dienophile.
• a conjugated diene such as, e.g., butadiene, piperylene, isoprene and chloroprene
• an optionally substituted alpha,beta-unsaturated aldehyde such as, e.g., a
• R1, R2 H (1,3-butadiene)
• R3, R4 H (acrolein)
• bicyclic unsaturated aldehydes may be obtained, as illustrated in the following scheme:
• Cycloaliphatic dicarboxaldehydes may also be prepared by hydroformylation of cyclic diolefins such as, e.g., cyclooctadiene, as described in, for example U.S. Patent No. 5,138,101 and DE 198 14 913, or by ozonolysis of bicyclic olefins such as norbornene to produce cyclopentane dicarboxaldehyde (see, e.g., Perry, /. Org. Chem., 42, 829-833, 1959). The entire disclosures of these three documents are incorporated by reference herein.
• products having a weight average molecular weight (Mw) of about 930 and a number average molecular weight (Mn) of about 730 and/or an average of about 6 hydroxy groups per molecule can routinely be produced.
• the process uses preferably a relatively high ratio of the number of aromatic hydroxyl groups to the number of aldehyde groups (e.g., about 6:1) to keep oligomerization low.
• the excess hydroxyaromatic compound may then be removed, for example, by distillation.
• the allylation of a cycloalkane tetraphenol such as, e.g., cyclohexane dicarboxaldehyde tetraphenol (and related phenolic compounds which may be present in admixture therewith) may be accomplished via a transcarbonation reaction using, for example, allyl methyl carbonate or a direct allylation reaction using, for example, an allyl halide, a methallyl halide, and the like plus an alkaline agent and an optional catalyst such as a phase transfer catalyst.
• a transcarbonation reaction using, for example, allyl methyl carbonate
• a direct allylation reaction using, for example, an allyl halide, a methallyl halide, and the like plus an alkaline agent and an optional catalyst such as a phase transfer catalyst.
• Allyl methyl carbonate is usually prepared from the reaction of allyl alcohol and dimethyl carbonate to afford a mixture of allyl methyl carbonate and diallyl carbonate. Both the crude mixture and the pure allyl methyl carbonate can be used as the allylating agent as well as allyl halides such as allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, and the like.
• a preferred process uses a transcarbonation reaction wherein allyl methyl carbonate is stoichiometrically reacted with a cycloalkane tetraphenol and provides an essentially total allylation of the hydroxy groups of the cycloalkane tetraphenol to provide the corresponding allylether (allyloxy) groups.
• an allyl halide may be stoichiometrically reacted with the hydroxy groups of the cycloalkane tetraphenol.
• variable amounts of Claisen rearrangement product may be observed in this reaction, resulting in mixtures of O- and C-allylated products.
• a direct allylation reaction of the cycloalkane tetraphenol with an allyl halide such as allyl chloride may, for example, be conducted in the presence of an alkaline agent such as an aqueous solution of an alkali metal hydroxide (e.g., NaOH).
• an alkaline agent such as an aqueous solution of an alkali metal hydroxide (e.g., NaOH).
• inert solvents such as, e.g., 1,4-dioxane
• phase transfer catalysts such as, e.g., benzyltrialkylammonium halides or tetraalkylammonium halides can be employed.
• Reaction temperatures of from about 25° to about 15O 0 C are operable with temperatures of from about 50° to about 100 0 C being preferred.
• reaction times of from about 15 minutes to about 8 hours are operable with reaction times of from about 2 hours to about 6 hours being preferred.
• a minor amount (about 20 percent or less) of the allyl groups will have undergone a thermally induced Claisen rearrangement and will thus be present on the aromatic ring ortho and/or para to the hydroxy groups from which the rearrangement occurred.
• the reaction of less than a 1 to 1 mole ratio of allyl methyl carbonate in the transcarbonation reaction or of allyl halide in the direct allylation reaction with the hydroxy groups of the tetraphenol will provide a partial allylation of the tetraphenol precursor with some free hydroxy groups remaining.
• these partially allylated cycloalkane tetraphenol compositions are less preferred, they are still useful in compositions of the present invention.
• the present invention also provides polymers (i.e., homo- and copolymers) and prepolymers (B-staged forms) of the ethylenically unsaturated monomers of formulae (I)/(Ia) and (II) set forth above (including the various aspects thereof).
• the homopolymers or copolymers of the monomers of the above formulae (I)/(Ia) and (II) may be prepared by heating with or without a free-radical forming catalyst and/or accelerator in the presence or absence of a solvent (preferably in the absence of a solvent). Temperatures of from about 12O 0 C to about 35O 0 C are typically employed in the homopolymerization with temperatures of from about 15O 0 C to about 25O 0 C being preferred.
• Suitable free radical forming catalysts which may optionally be used for the polymerization include those which are commonly employed in the free radical polymerization of ethylenically unsaturated monomers. Specific and non-limiting examples thereof include organic peroxides and hydroperoxides as well as azo and diazo compounds. Preferred examples of free radical forming catalysts include butyl peroxybenzoate, dicumyl peroxide, di-t-butylperoxide, mixtures thereof, and the like. The free radical forming catalysts may be employed, for example, at concentrations of from about 0.001 to about 2 percent by weight, based on the total weight of the monomers and/or prepolymers present.
• Suitable accelerators which may optionally be used for the polymerization include those which are commonly employed in the free radical polymerization of ethylenically unsaturated monomers. Specific and non-limiting examples thereof include the metal salts of organic acids. Preferred examples of accelerators include cobalt naphthenate and cobalt octoate. The accelerators may be employed, for example, at concentrations of from about 0.001 to about 0.5 percent by weight, based on the total weight of the monomers and/or prepolymers present.
• Partial homopolymerization (oligomerization or prepolymerization or B-staging) of the monomers of the above formulae (I)/(Ia) and (II) of the present invention may be effected, for example, by using lower polymerization temperatures and/or shorter polymerization reaction times than those indicated above.
• the curing of the prepolymerized monomers may then be completed at a later time or immediately following prepolymerization to comprise a single curing step.
• the progress of the (homo)polymerization can conveniently be followed by viscometry and/or infra-red spectrophotometric analysis and/or gel permeation chromatographic analysis.
• the ethylenically unsaturated monomers of the present invention may be copolymerized with a variety of other monomers and/or prepolymers.
• one or more monomers of formula (I)/(Ia) and/or (II) and/or prepolymers thereof may, for example, be present in amounts of from about 5 % to about 95 % by weight, e.g., from about 10 % to about 90 % by weight, or from about 25 % to about 75 % by weight, based on the total weight of the polymerizable components.
• Non-limiting examples of monomers and/or prepolymers which may be copolymerized with the monomers of formula (I)/(Ia) and/or prepolymers thereof and/or with the monomers of formula (II) and/or prepolymers thereof include allyl monomers and/or prepolymers thereof.
• Specific and non-limiting examples of the allyl monomers and prepolymers thereof include allyl-s-triazines, allyl ethers, allyl esters, diethylene glycol bis(allylcarbonate)s, allyl phenols, and phosphorus containing allyl monomers and prepolymers thereof.
• Preferred allyl monomers and/or prepolymers thereof for use in the present invention include triallyl isocyanurate, 2,4,6-tris(allyloxy)-s-triazine, hexaallylmelamine, hexa(allyloxymethyl)melamine, trimethylolpropane diallyl ether, 1,2,3- methallyloxypropane, o-diallyl bisphenol A, hexamethallyldipentaerythritol, diallyl phthalate, diallyl isophthalate, diethylene glycol bis(allylcarbonate), and allyl diphenyl phosphate.
• the allyl monomers and/or prepolymers may be used either individually or in any combination thereof.
• Non-limiting examples of dicyanates which may be copolymerized with the monomers of the present invention and/or prepolymers thereof include dicyanate compounds of the following formula (III) and/or prepolymers thereof:
• n, m and R and the cycloaliphatic moiety may have the same meanings (including exemplary and preferred meanings) as those set forth above with respect to formula (Ia).
• the compounds of formula (III) are more fully described in the co-assigned application entitled "AROMATIC DICYANATE COMPOUNDS WITH HIGH ALIPHATIC CARBON CONTENT", filed concurrently herewith (Attorney Docket No. 66499), the entire disclosure of which is expressly incorporated by reference herein.
• monomers (prepolymers) which may be copolymerized with the monomers (prepolymers) of the present invention include cyanate compounds of the above formula (III) wherein one of the cyano groups is replaced by an ethylenically unsaturated group such as, e.g., a group of formula wherein the moieties R 1 are defined as set forth above with respect to formula (I)/(Ia).
• cyanates which may be polymerized with the monomers of the present invention and/or prepolymers thereof include compounds of the following formula (IV) and/or prepolymers thereof:
• p, m, and R and the cycloaliphatic moiety may have the same meanings (including exemplary and preferred meanings) as those set forth above with respect to formula (II).
• at least two of the moieties Q represent -CN and the remaining moieties Q preferably represent hydrogen.
• at least three or all four moieties Q may represent -CN.
• Compounds of formula (IV) are more fully described in co-assigned application entitled "AROMATIC POLYCYANATE COMPOUNDS AND PROCESS FOR THE PRODUCTION THEREOF", filed concurrently herewith (Attorney Docket No. 66500), the entire disclosure of which is expressly incorporated by reference herein.
• the (co)polymerizable mixtures of the present invention and the products made therefrom respectively may further comprise one or more other substances such as, e.g., one or more additives which are commonly present in polymerizable mixtures and products made therefrom.
• additives include polymerization catalysts, co-curing agents, flame retardants, synergists for flame retardants, solvents, fillers, glass fibers, adhesion promoters, wetting aids, dispersing aids, surface modifiers, thermoplastic resins, and mold release agents.
• Non-limiting examples of co-curing agents for use in the present invention include dicyandiamide, substituted guanidines, phenolics, amino compounds, benzoxazine, anhydrides, amido amines, and polyamides.
• Non-limiting examples of catalysts for use in the present invention include transition metal complexes, imidazoles, phosphonium salts, phosphonium complexes, tertiary amines, hydrazides, "latent catalysts” such as Ancamine 2441 and K61B (modified aliphatic amines available from Air Products), Ajinomoto PN-23 or MY-24, and modified ureas.
• Non-limiting examples of flame retardants and synergists for use in the present invention include phosphorus containing molecules (DOP - epoxy reaction product), adducts of DOPO (6H-dibenz[c,e][l,2]oxaphosphorin-6-oxide), magnesium hydrate, zinc borate, and metallocenes.
• Non-limiting examples of solvents for use in the present invention include acetone, methylethyl ketone, and Dowanol® PMA
• Non-limiting examples of fillers for use in the present invention include functional and non-functional particulate fillers with a particle size range of from about 0.5 nm to about 100 ⁇ m. Specific examples thereof include silica, alumina trihydrate, aluminum oxide, metal oxides, carbon nanotubes, silver flake or powder, carbon black, and graphite.
• Non-limiting examples of adhesion promoters for use in the present invention include modified organosilanes (epoxidized, methacryl, amino, allyl, etc.), acetylacetonates, sulfur containing molecules, titanates, and zirconates.
• Non-limiting examples of wetting and dispersing aids for use in the present invention include modified organosilanes such as, e.g., Byk 900 series and W 9010, and modified fluorocarbons.
• Non-limiting examples of surface modifiers for use in the present invention include slip and gloss additives, a number of which are available from Byk-Chemie,
• thermoplastic resins for use in the present invention include reactive and non-reactive thermoplastic resins such as, e.g., polyphenylsulfones, polysulfones, polyethersulfones, polyvinylidene fluoride, polyetherimides, polyphthalimides, polybenzimidazoles, acrylics, phenoxy resins, and polyurethanes.
• mold release agents for use in the present invention include waxes such as, e.g., carnauba wax.
• the monomers of the present invention are useful, inter alia, as thermosettable comonomers for the production of printed circuit boards and materials for integrated circuit packaging (such as IC substrates). They are especially useful for formulating matrix resins for high speed printed circuit boards, integrated circuit packaging, and underfill adhesives. As a comonomer, they may also be used to adjust the amount of hydrocarbon in a thermoset matrix.
• the monomers of the present invention may be homopolymerized, for example using a free-radical forming catalyst and/or accelerator, to produce rigid, glassy polymers with an anticipated high degree of toughness, corrosion resistance, and moisture resistance.
• the utility for these homopolymers may be in the same applications that are served by poly[diethylene glycol bis(allyl carbonate)], also known as CR-39, and includes optical lenses, but with enhanced mechanical properties.
• reaction temperature reached 79 - 80 0 C.
• the reaction mixture was maintained for 8 hours at 77.5 - 80 0 C and then cooled to room temperature and vacuum filtered through a bed of diatomaceous earth packed on a medium fritted glass funnel.
• the recovered filtrate was rotary evaporated at a maximum oil bath temperature of 100 0 C and to a vacuum of 1.7 mm Hg pressure to provide a transparent, light yellow colored, liquid (35.04 grams) which became a tacky solid at room temperature.
• HPLC analysis revealed the presence of 96.78 area % allyl ether of l,l-bis(4- hydroxyphenyl)cyclododecane with the balance as a single minor component (3.22 area %).
• the single minor component was removed by dissolving the product in dichloromethane (100 milliliters) and passing the resultant solution through a 2 inch deep by 1.75 inch diameter bed of silica gel (230-400 mesh particle size, 60 angstrom mean pore size, 550 m 2 /gram surface dimension) supported on a medium fritted glass funnel. After elution from the silica gel bed with additional dichloromethane, a yellow band remained in the region of the origin. Rotary evaporation provided 33.98 grams (98.94 % isolated yield) of pale yellow colored tacky solid.
• HPLC analysis revealed the presence of 99.57 area % allyl ether of l,l-bis(4- hydroxyphenyl)cyclododecane with the balance as 2 minor components (0.22 and 0.21 area %).
• DSC Differential scanning calorimetry
• the isopropylidene diphenol assayed 99.72 area % via HPLC analysis with the balance consisting of 2 minor components (0.09 and 0.19 area %). Heating commenced and over the next 101 minutes, the reaction temperature reached 78°C.
• the reaction mixture was maintained for 8 hours at 78°C and then cooled to room temperature and vacuum filtered through a bed of diatomaceous earth packed on a medium fritted glass funnel.
• the recovered filtrate was rotary evaporated at a maximum oil bath temperature of 100 0 C and to a vacuum of 2.9 mm Hg pressure to provide a transparent, amber colored, liquid (25.21 grams) which remained liquid at room temperature.
• HPLC analysis revealed the presence of 95.25 area % allyl ether of isopropylidene diphenol with the balance as 12 minor components (ranging from 0.05 to 2.13 area %).
• the single minor component comprising 2.13 area % along with other minor components was removed by dissolving the product in dichloromethane (75 milliliters) and passing the resultant solution through a 2 inch deep by 1.75 inch diameter bed of silica gel (230-400 mesh particle size, 60 angstrom mean pore size, 550 m /gram surface dimension) supported on a medium fritted glass funnel. After elution from the silica gel bed with additional dichloromethane, a yellow band remained in the region of the origin.
• Triethylamine (10.17 grams, 0.1005 mole, 1.005 triethylamine : hydroxyl equivalent ratio) was added using a syringe in aliquots that maintained the reaction temperature at -5 to O 0 C. The total addition time for the triethylamine was 30 minutes. Addition of the initial aliquot of triethylamine induced haziness in the stirred solution with further additions inducing formation of a white slurry of triethylamine hydrobromide.
• the product slurry was added to a beaker of magnetically stirred deionized water (1.5 liters) providing an aqueous slurry. After 5 minutes of stirring, gravity filtration of the aqueous slurry through filter paper recovered the white powder product.
• the product from the filter paper was rinsed into a beaker using deionized water to a total volume of 200 milliliters, followed by the addition of dichloromethane (200 milliliters). A solution formed in the dichloromethane layer.
• the mixture was added to a separatory funnel, thoroughly mixed, allowed to settle, and then the dichloromethane layer recovered, with the aqueous layer discarded to waste. The dichloromethane solution was added back into the separatory funnel and extracted with fresh deionized water (200 milliliters) two additional times.
• HPLC analysis of a portion of the damp crystalline product revealed the presence of no detectable unreacted l,l-bis(4- hydroxyphenyl)cyclododecane, 1.02 area % monocyanate and 98.98 area % dicyanate.
• a second recrystallization of the damp crystalline product from acetone (40 milliliters) followed by drying in the vacuum oven at 50°C for 48 hours provided 20.12 grams of brilliant white product with no detectable unreacted l,l-bis(4- hydroxyphenyl)cyclododecane, 0.42 area % monocyanate and 99.58 area % dicyanate by HPLC analysis.
• l,l-Bis(4-cyanatophenyl)cyclododecane (0.5034 gram, 75 % wt.) and bis(allyl ether) of l,l-bis(4-hydroxyphenyl)cyclododecane (0.1678 gram, 25 % wt.) from Example 1 were weighed into a glass vial to which dichloromethane (1.5 milliliters) was added. HPLC analysis of the l,l-bis(4-cyanatophenyl)cyclododecane revealed 99.44 area % dicyanate and 0.56 area % monocyanate. Shaking the vial provided a solution which was added to an aluminum tray.
• Devolatilization conducted in a vacuum oven at 40°C for 30 minutes removed the dichloromethane giving a homogeneous blend.
• DSC analysis of portions (9.70 and 10.00 milligrams) of the blend was conducted using a rate of heating of 5°C per minute from 25°C to 400°C under a stream of nitrogen flowing at 35 cubic centimeters per minute.
• l,l-Bis(4-cyanatophenyl)cyclododecane (0.4004 gram, 75 % wt.) and bis(allyl ether) of isopropylidene diphenol (0.1335 gram, 25 % wt.) from Comparative Experiment A were weighed into a glass vial to which dichloromethane (1.5 milliliters) was added. HPLC analysis of the l,l-bis(4-cyanatophenyl)cyclododecane revealed 99.44 area % dicyanate and 0.56 area % monocyanate. Shaking the vial provided a solution which was added to an aluminum tray. Devolatilization conducted in a vacuum oven at 40°C for 30 minutes removed the dichloromethane giving a homogeneous blend.
• l,l-Bis(4-cyanatophenyl)cyclododecane (0.2978 gram, 50 % wt.) and bis(allyl ether) of l,l-bis(4-hydroxyphenyl)cyclododecane (0.2978 gram, 50 % wt.) from Example 1 were weighed into a glass vial to which dichloromethane (1.5 milliliters) was added.
• HPLC analysis of the l,l-bis(4-cyanatophenyl)cyclododecane revealed 99.44 area % dicyanate and 0.56 area % monocyanate. Shaking the vial provided a solution which was added to an aluminum tray. Devolatilization conducted in a vacuum oven at 40°C for 30 minutes removed the dichloromethane giving a homogeneous blend.
• HPLC analysis of the l,l-bis(4- cyanatophenyl)cyclododecane revealed 99.44 area % dicyanate and 0.56 area % monocyanate. Shaking the vial provided a solution which was added to an aluminum tray. Devolatilization conducted in a vented oven at 4O 0 C for 30 minutes removed the dichloromethane giving a homogeneous blend.
• HPLC analysis of the l,l-bis(4- cyanatophenyl)cyclododecane revealed 99.44 area % dicyanate and 0.56 area % monocyanate.
• Shaking the vial provided a solution which was added to a round aluminum pan.
• Devolatilization conducted in a vacuum oven at 50°C for 30 minutes removed the dichloromethane giving a homogeneous blend. Curing was conducted in ovens using the following curing schedule: 100 0 C for 1 hour, 15O 0 C for 1 hour, 200 0 C for 2 hours, 25O 0 C for 1 hour.
• a rigid, transparent, amber colored disk was recovered after curing and demolding from the aluminum pan.
• DSC analysis of portions (33.0 and 34.3 milligrams) of the cured product was conducted using a rate of heating of 5 0 C per minute from 25 0 C to 400 0 C under a stream of nitrogen flowing at 35 cubic centimeters per minute. Residual exothermicity was observed at >260°C and an average glass transition temperature of 181.83 0 C (185.8O 0 C and 177.85 0 C) (individual values in parenthesis) was measured. TGA of a portion (20.3110 milligrams) of the cured product was conducted using a rate of heating of 1O 0 C per minute from 25 0 C to 600 0 C under a dynamic nitrogen atmosphere.
• DSC analysis of portions (32.3 and 34.4 milligrams) of the cured product was conducted using a rate of heating of 5 0 C per minute from 25 0 C to 400 0 C under a stream of nitrogen flowing at 35 cubic centimeters per minute. Residual exothermicity was observed at >260°C and an average glass transition temperature of 133.16 0 C (134.03 0 C and 132.29 0 C) (individual values in parenthesis) was measured. TGA of a portion (6.3330 milligrams) of the cured product was conducted using a rate of heating of 1O 0 C per minute from 25 0 C to 600 0 C under a dynamic nitrogen atmosphere.
• the mixture was heated to 50 0 C with 500 rpm mechanical stirrer agitation.
• p-toluenesulfonic acid (PTSA) (1.3959 g total, 0.207% by weight) was added in six portions over 30 minutes.
• the temperature increased a few degrees with each PTSA addition.
• the temperature controller was set to 70 0 C and vacuum was applied to the reactor.
• the reactor pressure was gradually decreased to remove water from the reaction solution. When the reflux had stopped, the reactor was vented and water (48 g) was added.
• Ultraviolet spectrophotometric analysis provided a hydroxyl equivalent weight (HEW) of 118.64.
• High pressure liquid chromatographic (HPLC) analysis was adjusted to resolve 24 (isomeric) components present in the product.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Paints Or Removers (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=40640284

Family Applications (1)

Country Status (7)

Cited By (4)

Families Citing this family (8)

Citations (6)

Family Cites Families (12)

• 2009
  • 2009-03-09 EP EP09720009A patent/EP2265564A1/en not_active Withdrawn
  • 2009-03-09 KR KR1020107022649A patent/KR20100125400A/ko not_active Application Discontinuation
  • 2009-03-09 WO PCT/US2009/036522 patent/WO2009114466A1/en active Application Filing
  • 2009-03-09 JP JP2010550798A patent/JP6101418B2/ja not_active Expired - Fee Related
  • 2009-03-09 US US12/921,846 patent/US20110009560A1/en not_active Abandoned
  • 2009-03-09 CN CN200980117203.6A patent/CN102026950B/zh not_active Expired - Fee Related
  • 2009-03-11 TW TW098107844A patent/TWI490196B/zh not_active IP Right Cessation
• 2016
  • 2016-08-10 JP JP2016157237A patent/JP2017039919A/ja active Pending
  • 2016-09-12 JP JP2016177253A patent/JP2017031417A/ja active Pending

Patent Citations (6)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events